JP4113680B2 - Tetrathiafulvalene derivatives and methods for producing them - Google Patents
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- 0 CC(S*C*SS)=C(S)SC1(C2Sc3ccccc3SC12)S Chemical compound CC(S*C*SS)=C(S)SC1(C2Sc3ccccc3SC12)S 0.000 description 4
- YTELKVNHFJEBQH-YRNVUSSQSA-N C1OCCSS/C=C/OCCSC(SC(S2)=C3Sc4cc5ccccc5cc4S3)=C2SC1 Chemical compound C1OCCSS/C=C/OCCSC(SC(S2)=C3Sc4cc5ccccc5cc4S3)=C2SC1 YTELKVNHFJEBQH-YRNVUSSQSA-N 0.000 description 1
- CJJASMBNEGDQQV-UHFFFAOYSA-N SCCOCCSC(S1)=C(SCCOCCS)SC1=C1Sc(c(cccc2-c3c4c-5cccc4ccc3)c2c-5c2)c2S1 Chemical compound SCCOCCSC(S1)=C(SCCOCCS)SC1=C1Sc(c(cccc2-c3c4c-5cccc4ccc3)c2c-5c2)c2S1 CJJASMBNEGDQQV-UHFFFAOYSA-N 0.000 description 1
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、薄膜材料、例えばダイオード、トランジスター、電極材料、配線材料、回路形成材料、EL材料等として好適である、磁気異方性ユニットとなる芳香環及びチオール基又はジスルフィド基を有する新規なテトラチアフルバレン誘導体及びその製造方法に関する。
【０００２】
【従来の技術】
テトラチアフルバレン（ＴＴＦ）は強力な電子供与体であることが知られており、電子受容体であるテトラシアノキノジメタン（ＴＣＮＱ）と電荷移動錯体を形成して５５Ｋ以上で金属的な導電性を持つことが知られている。また、超導電性を示すビスエチレンジチオテトラチアフルバレン（ＢＥＤＴ−ＴＴＦ）のような機能性有機分子を電子デバイスとして組み込むことやその分子認識能を利用した応答性素子として利用する等の実用性デバイスとしての応用に関する研究も近年盛んに行われている。
また、金属や半導体表面における分子認識や分子集合体の構造に関する研究も盛んであり、有機分子の機能を最大限に発現させる実用デバイスを作るために必須となる、配向が制御された有機超薄膜を作製することが数多く研究されている。
一方、ＴＴＦ骨格にアルカンチオール基を導入したＴＴＦ誘導体について平滑な金基板上、あるいは金コロイド上に自己組織化膜（ＳＡＭ：Ｓｅｌｆ−Ａｓｓｅｍｂｌｅｄ Ｍｏｎｏｌａｙｅｒ）を形成するという研究も行われている（Ｃｈｅｍ．Ｃｏｍｍｕｎ．１９９９，７３７．；Ｌａｎｇｍｕｉｒ，１９９９，１５，８５７４）。しかしながら、高密度，高配向の有機薄膜を形成するまでには至っておらず、自己組織化膜材料として更なる展開が必要である。
一方、有機分子として、ベンゼンや、ナフタレン、アントラセン、フェナントレン、トリフェニレン、ピレン、ペリレンなどの多環芳香族化合物は、通常のものと比較して大きな磁気異方性を有することが知られている。また、これらの化合物については光導電性等の機能を持つことも知られおり、半導体などとして電子デバイスに応用しようとする試みも行われている。
【０００３】
【発明が解決しようとする課題】
このような事実からすれば、ベンゼン環などの芳香族化合物とＴＴＦ骨格の両方を兼ね備えた化合物は、光学的、電気的機能などの複合機能を同時に発現できることが期待され、また芳香環の磁気異方性を利用し、磁場中で薄膜を作製することにより、高密度、高配向の超薄膜が形成されることが期待される。
そこで、本発明の目的は、磁気異方性ユニットとなる芳香環、及びチオール基又はジスルフィド基を組み込んだ新規なテトラチアフルバレン誘導体を提供することにあり、更にそれを薄膜材料として用いることにより磁場中で高密度、高配向な薄膜を作製する方法を提供することにある。
【０００４】
【課題を解決するための手段】
上述の目的を達成するため、本発明（請求項１）は、
一般式（２）
【化６】
一般式（３）
【化７】
又は
【化８】
一般式（１）
【化５】
で表わされるテトラチアフルバレン誘導体の製造方法である。
また、本発明（請求項２）は、
一般式（１）
【化５】
で表わされるテトラチアフルバレン誘導体である。
【０００５】
また、本発明（請求項３）は、基板上に請求項２に記載のテトラチアフルバレン誘導体を被覆した磁気異方性を有することを特徴とするテトラチアフルバレン誘導体の薄膜体である。
また、本発明（請求項４）は、
一般式（１）
【化５】
また、本発明（請求項５）は、請求項３または４に記載のテトラチアフルバレン誘導体の薄膜を作製するに際し、薄膜の作成を一定方向の磁場をかけて行うことを特徴とするテトラチアフルバレン誘導体の薄膜の製造方法である。
【０００６】
【発明の実施の態様】
本発明のテトラチアフルバレン誘導体（以下本発明化合物という）は、上記化合物（１）で表わされるが、当該一般式（１）中の芳香族環とは式
【化９】
また、芳香族環に置換しているＲ１としては、プロトン、メチル基・エチル基等のアルキル基、メトキシ基・エトキシ基等のアルコキシが挙げられ、これらが、当該一般式（１）中の芳香族環に複数個置換していてもよい。
【０００７】
本発明の請求項１、請求項２の化合物の具体例としては、例えば以下のようなもの等が挙げられる。
【化１０】
【化１２】
【化１４】
【化４０】
本発明化合物は、一般式（２）で表わされるチオン類又はケトン類と、一般式（３）又は一般式（４）で表わされるケトン類を反応させることにより得られる。
反応は芳香族炭化水素溶媒、ＴＨＦ、アセトニトリル、ＤＭＦ、二流化炭素、水、トリエチルホスファイト、酢酸、クロロホルム等のハロゲン化水素溶媒、アルコール系溶媒など適切な溶媒を用い、開放系もしくは不活性ガス気流下で行ったものである。好適反応温度は−３０℃ないし２５０℃、より好ましくは０℃ないし１５０℃である。
原料化合物の一般式（２）で表されるチオン類は、一般式
【化６６】
【化６７】
【０００９】
また、本発明は、前記一般式（１）のテトラチアフルバレン誘導体を基板上に被覆した薄膜体を提供するものである。
このような薄膜体は、ダイオード、トランジスター、電極材料、配線材料、回路形成材料、ＥＬ材料等として好適である。
薄膜の製造方法としては、前記一般式（１）の化合物を真空蒸着する気相法や、溶液にする湿式法での自己組織化による方法などが挙げられる。
また、前記一般式（１）のテトラチアフルバレン誘導体を用いて薄膜を製造するにあたり、一定方向の磁場中で行うのが高密度、高配向のものが得られるので好ましい。
【００１０】
【実施例】
次に、本発明を実施例によりさらに詳細に説明するが、なお本発明はこれらの例によって何ら限定されるものではない。
【００１１】
原料化合物の一般式（２）で表されるチオン類の合成について示す。
［合成例１］
枝付き５００ｍｌのナスフラスコに窒素気流下Ｎ，Ｎ，Ｎ´，Ｎ´−テトラメチレンジアミン１１１ｍｌ（７４４ｍｍｏｌ）、ｎ−ヘキサン３００ｍｌを加え攪拌し、ｎ−ブチルリチウム３００ｍｌ（７４４ｍｍｏｌ）を加えて更に攪拌した。０℃に冷却したこのリアクターに、窒素気流下、枝付きジョイント付き２００ｍｌフラスコ中のチオフェノール３４．１１ｍｌ（３３８ｍｍｏｌ）のｎ−ヘキサン溶液１５０ｍｌをキャヌラーで滴下した。滴下後室温にて２４時間攪拌した。次いで０℃に冷却した後、単体硫黄２３．８６ｇ（７４４ｍｍｏｌ）を添加して室温にて１２時間攪拌した。ロータリーエバポレーターにて溶媒を除去した後、予備乾燥したＴＨＦ２００ｍｌに溶解し、０℃に冷却してリチウムアルミニウムハイドライド１０ｇで還元し、そのまま油浴にて還流した。２時間後、溶液を氷水の入ったビーカーにゆっくり注ぎ込み、エーテルおよび濃塩酸にて洗浄し、酸性条件下で抽出を行い、水相を除去した。分液ロートに残った有機相に水酸化ナトリウム水溶液（１Ｎ）を加え塩基性条件下で抽出を行った。この際、分離した水相を５００ｍｌのナスフラスコに加え水酸化ナトリウム６ｇと二硫化炭素８０ｍｌを加えて浴温６０℃で還流した。６時間後浴温を１００℃まで上げて、分別還流リアクターのコックを開いて二硫化炭素を完全に除去した。室温まで冷却した後、吸引ろ過にて結晶をろ別し、水で赤みが消えるまで洗浄した。吸引ポンプにて１００℃で４時間乾燥し水を除去して１，３−ベンゾジチオール−２−チオン５５．８４ｇ（９０％）を黄色粉末として得た。この化合物の物性を以下に示す。
融点：１６５．３−１６６．２℃；
１ＨＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）：δ７．３８−７．５０（ｍ，４Ｈ，Ａｒ−Ｈ）；
１３ＣＮＭＲ（１０１ＭＨｚ，ＣＤＣｌ３）：δ１２１．８，１２７．４，１４１．３，２１１．８；
ＵＶ（ＣＨＣｌ３）（λｍａｘ（ｌｏｇε））：２９１．０ｎｍ（４．１１），３６５．５ｎｍ（４．７６）．
【００１２】
［合成例２］
乾燥した金属マグネシウム１．０９４ｇ（４５ｍｍｏｌ）を窒素置換した１００ｍｌの三口フラスコに入れ、無水ＴＨＦ８ｍｌを加えて超音波にかけた。開始剤となるエチレンジブロミドを数滴加え反応確認後、窒素置換した５０ｍｌの枝付きフラスコに準備した９−ブロモフェナントレン７．７８４ｇ（３０ｍｍｏｌ）のＴＨＦ溶液３０ｍｌをキャヌラーにて滴下した。反応終了後、０℃に冷却し単体硫黄１．４５５ｇ（４５ｍｍｏｌ）を添加し１２時間室温にて攪拌した。氷水の入ったビーカーに注ぎ込み、濃塩酸にて残ったマグネシウムを溶解した。吸引ろ過により沈殿を分離し、ろ液は塩化メチレンで抽出し硫酸マグネシウムで乾燥し、ろ過してロータリーエバポレーターにより濃縮し、ろ塊と一緒に予備乾燥したＴＨＦ１５０ｍｌに溶解した。０℃に冷却し、リチウムアルミニウムハイドライド２ｇを加え２時間還流して、氷水の入ったビーカーに注ぎ込み濃塩酸にてｐＨ１にしてエーテルとＴＨＦの混合溶媒で抽出し、水相を除去した。得られた有機相に１Ｎの水酸化ナトリウム水溶液を適当量加えて抽出し、有機相を除去した。分離した水相に再び濃塩酸を加え、塩化メチレンにて抽出し、硫酸マグネシウムで乾燥し、ろ過し、ロータリーエバポレーターにより濃縮して、クロロホルムを展開溶媒としたシリカゲルカラムクロマトグラフィー（φ＝５．０ｃｍ，ｈ＝３ｃｍ）により分離精製して９−メルカプトフェナントレン５．０４ｇ（８０％）を無色粉末として得た。この化合物の物性を以下に示す。
融点：９７．０−９８．０℃；
１ＨＮＭＲ（６０ＭＨｚ，ＣＤＣｌ３）：δ３．６１（ｓ，１Ｈ，ＳＨ），７．４８−７．８５（ｍ，６Ｈ，Ａｒ−Ｈ），８．１４−８．３６（ｍ，１Ｈ，Ａｒ−Ｈ），８．４５−８．８３（ｍ，２Ｈ，Ａｒ−Ｈ）；
ＩＲ（ＫＢｒ）：２５６６（ＳＨ）ｃｍ−１
【００１３】
枝付きジョイントを組み込んだ５００ｍｌのナスフラスコに窒素気流下９−メルカプトフェナントレン１４．７２ｇ（７０ｍｍｏｌ）、ｃ−ヘキサン２５０ｍｌおよびＮ，Ｎ，Ｎ’，Ｎ’−テトラメチレンジアミン２３．１ｍｌ（１５４ｍｍｏｌ）を加え攪拌し、０℃に冷却した後、ｎ−ブチルリチウム／ｎ−ヘキサン溶液６２．６ｍｌ（１５４ｍｍｏｌ）を加えて室温にて２４時間攪拌した。更に０℃に冷却した後、単体硫黄４．９４ｇ（１５４ｍｍｏｌ）を添加して室温にて１２時間攪拌した。ロータリーエバポレーターにて溶媒を除去した後、予備乾燥したＴＨＦ３００ｍｌに溶解し０℃に冷却してリチウムアルミニウムハイドライド１０．０ｇで還元し、そのまま油浴にて還流した。２時間後、氷水の入ったビーカーにその溶液をゆっくり注ぎ込み、エーテルおよび濃塩酸にて洗浄し、酸性条件下で抽出を行い、水相を除去した。分液ロートに残った有機相に水酸化ナトリウム水溶液（５Ｎ）を加え塩基性条件下で抽出した。この際、分離した水相を５００ｍｌのナスフラスコに加え水酸化ナトリウム６ｇと二硫化炭素８０ｍｌを加えて浴温６０℃で還流した。２時間後浴温を１００℃まで上げて、分別還流リアクターのコックを開いて二硫化炭素を完全に除去した。このことにより水相に黄色の結晶が析出するので吸引ろ過にて結晶をろ別し、水で充分に洗浄した。吸引ポンプにて１００℃で２時間乾燥し、水を除去した。クロロホルムを加えて懸濁溶液にし、吸引ろ過にて結晶をろ別し、クロロホルムで充分に洗浄した。この操作で回収したろ液は濃縮して数回同様の方法にて結晶を取り出した。分離した結晶は大量のジクロロメタンを加え懸濁中でろ過カラム処理を行った。濃縮・乾燥してフェナントロ［９，１０−ｄ］１，３−ジチオーレン−２−チオン１．０５ｇ（１２％）を黄色粉末として得た。この化合物の物性を以下に示す。
融点：２４５．９−２４６．５℃；
１ＨＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）：δ７．６５−７．７５（ｍ，６Ｈ，Ａｒ−Ｈ），８．６８−８．７０（ｍ，２Ｈ，Ａｒ−Ｈ）；
１ＨＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３：ＣＳ２＝１：１０（ｖｏｌ））：δ７．５９−７．６９（ｍ，６Ｈ，Ａｒ−Ｈ），８．５９−８．６２（ｍ，２Ｈ，Ａｒ−Ｈ）；
１３ＣＮＭＲ（１０１ＭＨｚ，ＣＤＣｌ３：ＣＳ２＝１：１０（ｖｏｌ））：δ６７．４，１２３．３（２Ｃ），１２５．４（２Ｃ），１２５．７，１２７．４（２Ｃ），１２７．７（２Ｃ），１２９．１（２Ｃ），１３６．７（２Ｃ）；
ＩＲ（ＫＢｒ）：１６０５，１５６２，１４９０，１４３２，１２６２，１０５８，８０３，７３２，７１７，５５９，５１９，４３９，４３６ｃｍ−１；
ＭＳｍ／ｚ２８４（Ｍ＋）；Ａｎａｌ．Ｃａｌｃｄ．ｆｏｒＣ１５Ｈ８Ｓ３：Ｃ，６３．３４；Ｈ，２．８４％．Ｆｏｕｎｄ：Ｃ，６３．６３；Ｈ，２．８１％。
【００１４】
原料化合物の一般式（３）で表されるケトン類の合成について示す。
［合成例３］
窒素置換したフラスコに、ナトリウム４．６ｇ（２００ｍｍｏｌ）と二硫化炭素３６ｍｌ（７７２ｍｍｏｌ）を加え３０分還流してナトリウムを活性化した後、ＤＭＦ４０ｍｌを加えて再び２時間還流した後、６０℃以下の油浴で減圧蒸留して溶媒を除去した。次いで生成物をメタノール１２０ｍｌと水６０ｍｌに溶解し、塩化亜鉛４ｇ（２９．４ｍｍｏｌ）とアンモニア水７５ｍｌを加え、臭化テトラエチルアンモニウム１０．６ｇ（５０．４ｍｍｏｌ）の水溶液を加えて、室温で１２時間攪拌し、吸引ろ過して得た生成物を８０℃で１２時間減圧乾燥してビス（テトラエチルアンモニウム）ビス（２−チオキソ−１，３−ジチオール−４，５−ジチオレート）ジンケート１５．９５ｇ（８８％）を暗赤色結晶として得た。この亜鉛錯体化合物の物性を以下に示す。
融点：１９８．７−２００．１℃；
ＩＲ（ＫＢｒ）：２９７９，１４５８，１４１７，１１８２，１０５９，１０３８，９９６，８８８，７８５ｃｍ−１
【００１５】
アセトニトリル２５ｍｌに、上記亜鉛錯体化合物１．４４ｇ（２ｍｍｏｌ）と３−ブロモプロピオニトリル１．３４ｇ（１０ｍｍｏｌ）を加え１時間還流した。次いで室温まで冷やし、吸引ろ過により黒色の沈殿を除去し、ロータリーエバポレーターにて溶媒を除去した後、再び塩化メチレンに溶かして抽出した。乾燥剤にて残留水分を除去し、乾燥剤をろ別してロータリーエバポレーターにて濃縮した。塩化メチレン／ｎ−ヘキサンにて再結晶して、吸引ろ過したものを吸引ポンプで３０分乾燥して４，５−ビス（２−シアノエチルチオ）−１，３−ジチオール−２−チオン１．０１ｇ（８３％）を赤色針状晶として得た。この化合物の物性を以下に示す。
融点８２．４−８３．３℃；
１ＨＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）：δ２．８１（ｔ，Ｊ＝６．９Ｈｚ，４Ｈ，ＣＨ２），３．１７（ｔ，Ｊ＝６．９Ｈｚ，４Ｈ，ＣＨ２）；
１３ＣＮＭＲ（１０１ＭＨｚ，ＣＤＣｌ３）：δ１９．０，３１．８，１１７．１，１３５．８，２０９．１；
ＩＲ（ＫＢｒ）：２９７７，２２４８，１４５８，１４１１，１２９０，１０７１，８９４ｃｍ−１
【００１６】
上記４，５−ビス（２−シアノエチルチオ）−１，３−ジチオール−２−チオンをアセトニトリルに溶解した溶液に、水酸化セシウム１．２６ｇ（８．４ｍｍｏｌ）をメタノール１２ｍｌに溶解した溶液を攪拌しながらゆっくりと滴下しさらに攪拌した。滴下終了後３０分経過した後、ヨウ化メチル１１．３６ｇ（４０ｍｍｏｌ）を加え再び３０分攪拌した。過剰のヨウ化メチルを除去するため、窒素を３０分間吹き込みロータリーエバポレーターにて濃縮した。この濃縮物を塩化メチルに溶かして抽出し、乾燥剤を加えて残りの水を除去したのち、ろ別した。次いでロータリーエバポレーターにて濃縮し、クロロホルムを展開溶媒としてシリカゲルカラムクロマトグラフィー（φ＝５．５ｃｍ，ｈ＝１６ｃｍ）により分離精製して４−（２−シアノエチルチオ）−５−メチルチオ−１，３−ジチオール−２−チオン１．７８ｇ（８４％）を黄色針状晶として得た。この化合物の物性を以下に示す。
融点９０．０−９１．１℃；
１ＨＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）：δ２．５６（ｓ，３Ｈ，ＣＨ３），２．７５（ｔ，Ｊ＝７．１Ｈｚ，２Ｈ，ＣＨ２），３．０９（ｔ，Ｊ＝７．１Ｈｚ，２Ｈ，ＣＨ２）；
１３ＣＮＭＲ（１０１ＭＨｚ，ＣＤＣｌ３）：δ１８．８，１８．９，３１．８，１１７．１，１２６．０，１４４．９，２０９．９；
ＩＲ（ＫＢｒ）：２２４７，１４６４，１４３８，１４１６，１３１８，１２７６，１０５４，９５３，９００ｃｍ−１
【００１７】
［合成例４］
４−（２−シアノエチルチオ）−５−メチルチオ−１，３−ジチオール−２−チオン１．５９ｇ（６ｍｍｏｌ）を窒素置換し、クロロホルム／酢酸（３：１）の混合溶媒２５ｍｌに溶かし、これに固体添加装置を用いて窒素置換した酢酸水銀５ｇ（１６ｍｍｏｌ）を加え、１６時間攪拌後、吸引ろ過によりろ液を分離した。これをビーカーに注ぎ、飽和炭酸水素ナトリウム水溶液で中和後、分液ロートで抽出した。乾燥剤にて残りの水を除去し、ろ別した。ロータリーエバポレーターにて濃縮し、吸引ポンプで乾燥して４−（２−シアノエチルチオ）−５−メチルチオ−１，３−ジチオール−２−オン１．５７ｇを定量的に黄色針状晶として得た。この化合物の物性を以下に示す。
融点６１．８−６２．５℃；
１ＨＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）：δ２．５２（ｓ，３Ｈ，ＣＨ３），２．７４（ｔ，Ｊ＝７．１ Ｈｚ，２Ｈ，ＣＨ２），３．０７（ｔ，Ｊ＝７．１Ｈｚ，２Ｈ，ＣＨ２）；
１３ＣＮＭＲ（１０１ＭＨｚ，ＣＤＣｌ３）：δ１８．８，１９．１，３１．６，１１７．２，１１８．０，１３５．６，１８８．７；
ＩＲ（ＫＢｒ）：２９２２，２２４６，１７７７，１６６１，１６１８，１４１３，１２７４，９５７，８９９，７４７ｃｍ−１
【００１８】
［合成例５］
４，５−ビス（２−シアノエチルチオ）−１，３−ジチオール−２−チオン０．９１３ｇ（３ｍｍｏｌ）を窒素置換し、クロロホルム／酢酸（３：１）混合溶媒２５ｍｌに溶かした。酢酸水銀２．５００ｇ（８ｍｍｏｌ）を固体添加装置を用いて加え、１６時間攪拌後、吸引ろ過によりろ液を分離した。これをビーカーに注ぎ、飽和炭酸水素ナトリウム水溶液で中和後、分液ロートで抽出した。乾燥剤にて残りの水を除去し、これをろ別した。ロータリーエバポレーターにて濃縮し、吸引ポンプで乾燥して４，５−ビス（２−シアノエチルチオ）−１，３−ジチオール−２−オン０．９２１ｇを定量的に深黄色針状晶として得た。この化合物の物性を以下に示す。
融点：６２．８−６４．２℃；
１ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）：δ２．８０（ｔ，Ｊ＝６．９Ｈｚ，４Ｈ，ＣＨ２），３．１４（ｔ，Ｊ＝６．９Ｈｚ，４Ｈ，ＣＨ２）；
１３ＣＮＭＲ（１０１ＭＨｚ，ＣＤＣｌ３）：δ１９．０，３１．６，１１７．２，１２７．４，１８７．６；
ＩＲ（ＫＢｒ）：２９５１，２２４９，１７７５，１６６６，１６１５，１４２０，１２８３，１１５６，８８６，７４１ｃｍ−１
【００１９】
［実施例１］
合成例１で得た１，３−ベンゾジチオール−２−チオン０．９２ｇ（５ｍｍｏｌ）と合成例４で得た４−（２−シアノエチルチオ）−５−メチルチオ−１，３−ジチオール−２−オン１．４２ｇ（５ｍｍｏｌ）を窒素置換し、トリエチルホスファイト６．４ｍｌを加えて１２０℃で１．５時間攪拌した。反応溶液を室温まで冷やし、結晶を吸引ろ過により分離してメタノールで洗浄した。クロロホルムを展開溶媒としてシリカゲルカラムクロマトグラフィー（φ＝３．０ｃｍ，ｈ＝３ｃｍ）により分離精製して４−（２−シアノエチルチオ）−５−メチルチオ−ベンゾテトラチアフルバレン１．０６ｇ（６８％）を橙色針状晶として得た。この化合物の物性を以下に示す。
尚、一般式（２）で表される１，３−ベンゾジチオール−２−オンと合成例４で得た４−（２−シアノエチルチオ）−５−メチルチオ−１，３−ジチオール−２−オンとの反応でも、同様に４−（２−シアノエチルチオ）−５−メチルチオベンゾテトラチアフルバレンを１８％の収率で得ることができる。
融点１２８．５−１２９．４℃；
１ＨＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）：δ２．４８（ｓ，３Ｈ，ＣＨ３），２．７０（ｔ，Ｊ＝７．２Ｈｚ，４Ｈ，ＣＨ２），３．０３（ｔ，Ｊ＝７．２Ｈｚ，４Ｈ，ＣＨ２），７．１１−７．２７（ｍ，４Ｈ，Ａｒ−Ｈ）；
１３ＣＮＭＲ（１０１ＭＨｚ，ＣＤＣｌ３）：δ１８．７，１９．１，３１．２，１０８．５，１１３．４，１１７．５，１２０．０，１２１．９１，１２１．９３，１２６．０２，１２６．０３，１３５．１，１３６．２，１３６．３；
ＩＲ（ＫＢｒ）：２９２０，２２４６，１４９３，１４４４，１４１５，１２７２，１１２０，８９６，７７４，７４１，７３１，６７４ｃｍ−１
ＭＳｍ／ｚ３８５（Ｍ＋）；
Ａｎａｌ．Ｃａｌｃｄ．ｆｏｒＣ１４Ｈ１１ＮＳ６：Ｃ，４３．６０；Ｈ，２．８８；Ｎ，３．６３％．Ｆｏｕｎｄ：Ｃ，４３．２４；Ｈ，２．８７；Ｎ，３．６７％．
【００２０】
上記４−（２−シアノエチルチオ）−５−メチルチオ−ベンゾテトラチアフルバレン７７１ｍｇ（２ｍｍｏｌ）のＴＨＦ溶液２０ｍｌに１，８−ジブロモオクタン１．８４ｍｌ（１０ｍｍｏｌ）を加え、水酸化セシウム４５０ｍｇ（３ｍｍｏｌ）をメタノール１０ｍｌに溶かした溶液を攪拌しながら滴下し３時間室温にて攪拌した。塩化メチレンに溶かして抽出し、乾燥剤を加えて残りの水を除去しろ別した。引き続きロータリーエバポレーターにて濃縮して、クロロホルム：ｎ−ヘキサン（＝１：２）を展開溶媒としたシリカゲルカラムクロマトグラフィー（φ＝３．５ｃｍ，ｈ＝１０ｃｍ）およびゲルろ過クロマトグラフィーにより分離精製して４−（８−ブロモオクチルチオ）−５−メチルチオ−ベンゾテトラチアフルバレン８９０ｍｇ（８５％）を橙色油状物として得た。この化合物の物性を以下に示す。
１ＨＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）：δ１．３０−１．８６（ｍ，１２Ｈ，ＣＨ２），２．４３（ｓ，３Ｈ，ＣＨ３），２．８１（ｔ，Ｊ＝７．２Ｈｚ，２Ｈ，ＣＨ２），３．３９（ｔ，Ｊ＝６．８Ｈｚ，２Ｈ，ＣＨ２），７．１０−７．２５（ｍ，４Ｈ，Ａｒ−Ｈ）；
１３ＣＮＭＲ（１０１ＭＨｚ，ＣＤＣｌ３）：δ１９．２，２８．０，２８．２，２８．６，２８．８，３０．０，３２．７，３４．０，３６．２，１１０．１，１１１．３，１２１．９，１２５．８，１２５．９，１３６．４８，１３６．５３；
ＩＲ（ｎｅａｔ）：２９２７，２８５３，１４４７，７７４，５５９ｃｍ−１；
ＭＳｍ／ｚ５２３（Ｍ＋）；
Ａｎａｌ．Ｃａｌｃｄ．ｆｏｒＣ１９Ｈ２３ＢｒＳ６：Ｃ，４３．５８；Ｈ，４．４３％．Ｆｏｕｎｄ：Ｃ，４３．５３；Ｈ，４．６９％．
【００２１】
上記４−（８−ブロモオクチルチオ）−５−メチルチオ−ベンゾテトラチアフルバレン２６２ｍｇ（０．５ｍｍｏｌ）のＴＨＦ溶液２０ｍｌを玉突き冷却環を備えた５０ｍｌ枝付きフラスコに加え、さらにチオ尿素１９１ｍｇ（２．５ｍｍｏｌ）の水溶液５ｍｌを加えて２４時間還流した後、さらに水酸化ナトリウム３００ｍｇ（１５ｍｍｏｌ）の水溶液５ｍｌを加え２時間還流した。生成物を塩化メチレンに溶かして酸性条件下で有機相を抽出し、乾燥剤を加えて残りの水を除去してろ別した。引き続きロータリーエバポレーターにて濃縮し、クロロホルム：ｎ−ヘキサン（１：２）を展開溶媒としたシリカゲルカラムクロマトグラフィー（φ＝３．０ｃｍ，ｈ＝５ｃｍ）およびゲルろ過カラムクロマトグラフィーにより分離精製して４−（８−メルカプトオクチルチオ）−５−メチルチオ−ベンゾテトラチアフルバレン１５１ｍｇ（６３．３％）を橙色油状物として得た。この化合物の物性を以下に示す。
１ＨＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）：δ１．２９−１．６６（ｍ，１３Ｈ，ＣＨ２，ＳＨ），２．４３（ｓ，３Ｈ，ＣＨ３），２．５１（ｑ，Ｊ＝７．２Ｈｚ，２Ｈ，ＣＨ２），２．８２（ｔ，Ｊ＝７．２Ｈｚ，２Ｈ，ＣＨ２），７．１０−７．２６（ｍ，４Ｈ，Ａｒ−Ｈ）；
１３ＣＮＭＲ（１０１ＭＨｚ，ＣＤＣｌ３）：δ１９．２，２４．６，２８．２，２８．３，２８．８８，２８．９１，２９．６，３４．０，３６．２，９６．１，１１０．２，１１１．３，１２１．９，１２５．９，１２９．３，１３６．５１，１３６．５５；
ＩＲ（ｎｅａｔ）：２９２５，２８５２，２５６３，１４４６，７７４，５５９ｃｍ−１；
ＭＳｍ／ｚ４７６（Ｍ＋）；
Ａｎａｌ．Ｃａｌｃｄ．ｆｏｒＣ１９Ｈ２４ＮＳ７：Ｃ，４７．８６；Ｈ，５．０７％．Ｆｏｕｎｄ：Ｃ，４７．５７；Ｈ，５．１１％．
【００２２】
［実施例２］
合成例１で得た１，３−ベンゾジチオール−２−チオン０．９２２ｇ（５ｍｍｏｌ）と合成例５で得た４，５−ビス（２−シアノエチルチオ）−１，３−ジチオール−２−オン１．４２２ｇ（５ｍｍｏｌ）とを窒素置換し、トリエチルホスファイト６．４ｍｌを加えて１２０℃で１．５時間攪拌した。反応溶液を室温まで冷やし、結晶を吸引ろ過により分離してメタノールで洗浄した。クロロホルムを展開溶媒としてシリカゲルカラムクロマトグラフィー（φ＝３．０ｃｍ，ｈ＝３ｃｍ）により分離精製して４，５−ビス（２−シアノエチルチオ）−ベンゾテトラチアフルバレン０．８２９ｇ（３９％）を橙色針状晶として得た。この化合物の物性を以下に示す。
融点：１４７．２−１４８．０℃；
１ＨＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）：δ２．７４（ｔ，Ｊ＝７．１Ｈｚ，４Ｈ，ＣＨ２），３．０９（ｔ，Ｊ＝７．１Ｈｚ，４Ｈ，ＣＨ２），７．１３−７．２８（ｍ，４Ｈ，Ａｒ−Ｈ）；
１３ＣＮＭＲ（１０１ＭＨｚ，ＣＤＣｌ３）：δ１８．８，３１．２，１０６．９，１１５．４，１１７．４，１２２．０，１２６．１，１２７．９，１３６．１；
ＩＲ（ＫＢｒ）２９２５，２２５１，１４２６，１１１９，８９２，７３５ｃｍ−１；
ＭＳｍ／ｚ４２４（Ｍ＋）；
Ａｎａｌ．Ｃａｌｃｄ．ｆｏｒＣ１６Ｈ１２Ｎ２Ｓ６：Ｃ，４５．２５；Ｈ，２．８５；Ｎ，６．６０％．Ｆｏｕｎｄ：Ｃ，４５．０４；Ｈ，２．８１；Ｎ，６．５２％．
【００２３】
上記４，５−ビス（２−シアノエチルチオ）−ベンゾテトラチアフルバレン４２５ｍｇ（１ｍｍｏｌ）のＴＨＦ溶液３０ｍｌに１，８−ジブロモオクタン３．６８ｍｌ（２０ｍｍｏｌ）を加え、メタノール５ｍｌに溶かした水酸化セシウム３３０ｍｇ（５ｍｍｏｌ）を攪拌しながら滴下し２時間室温にて攪拌した。塩化メチレンに溶かして抽出し，乾燥剤を加えて残りの水を除去してろ別した。引き続きロータリーエバポレーターにて濃縮して、クロロホルム：ｎ−ヘキサン（＝１：２）を展開溶媒としたシリカゲルカラムクロマトグラフィー（φ＝３．５ｃｍ，ｈ＝１０ｃｍ）およびゲルろ過クロマトグラフィーにより分離精製して４，５−ビス（８−ブロモオクチルチオ）−ベンゾテトラチアフルバレン５４１ｍｇ（７７％）を橙色油状物として得た。この化合物の物性を以下に示す。
１ＨＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）：δ１．３２−１．８７（ｍ，２４Ｈ，ＣＨ２），２．８８（ｔ，Ｊ＝７．３Ｈｚ，４Ｈ，ＣＨ２），３．３８（ｔ，Ｊ＝６．８Ｈｚ，４Ｈ，ＣＨ２），７．０９−７．２６（ｍ，４Ｈ，Ａｒ−Ｈ）；
１３ＣＮＭＲ（１０１ＭＨｚ，ＣＤＣｌ３）：δ２８．１，２８．４，２８．７，２８．９，２９．８，３２．８，３４．０，３６．５，１２１．８７，１２１．９１，１２５．９，１２６．０，１３１．７，１３６．５，１３６．６；
ＭＳｍ／ｚ７００（Ｍ＋）；
Ａｎａｌ．Ｃａｌｃｄ．ｆｏｒＣ２６Ｈ３６Ｂｒ２Ｓ６：Ｃ，４４．５６；Ｈ，５．１８％．Ｆｏｕｎｄ：Ｃ，４４．３７；Ｈ，５．４４％．
【００２４】
上記４，５−ビス（８−ブロモオクチルチオ）−ベンゾテトラチアフルバレン７０１ｍｇ（１ｍｍｏｌ）のＴＨＦ２０ｍｌ溶液に、チオ尿素７６１ｍｇ（５ｍｍｏｌ）の水溶液５ｍｌを加え、８０℃の油浴で２４時間攪拌した後、水酸化ナトリウム１．２ｍｇ（３０ｍｍｏｌ）の水溶液１０ｍｌを加え２時間還流を行った。ロータリーエバポレーターにてある程度濃縮した後、酸性条件下で塩化メチレンに溶かして抽出し、乾燥剤を加えて残りの水を除去してろ別した。この塩化メチレン反応溶液５０ｍｌをヨウ素、及びトリエチルアミンの塩化メチレン溶液を滴下して酸化し、亜硫酸水素ナトリウム水溶液にて抽出した。ロータリーエバポレーターにて濃縮して、クロロホルム：ｎ−ヘキサン（１：３）を展開溶媒としたシリカゲルカラムクロマトグラフィー（φ＝３．５ｃｍ，ｈ＝１０ｃｍ）および、クロロホルム：メタノールにより再結晶して分離精製し、化合物（６）（ｎ＝８）で示されるベンゾテトラチアフルバレン誘導体７４ｍｇ（１２％）を橙色針状晶として得た。この化合物の物性を以下に示す。
融点：８３．９−８４．２℃；
１ＨＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）：δ１．３２−１．７１（ｍ，２４Ｈ，ＣＨ２），２．６６（ｔ，Ｊ＝７．３Ｈｚ，４Ｈ，ＳＳ−ＣＨ２），３．３９（ｔ，Ｊ＝７．３Ｈｚ，４Ｈ，ＣＳ−ＣＨ２），７．１０−７．２６（ｍ，４Ｈ，Ａｒ−Ｈ）；
１３ＣＮＭＲ（１０１ＭＨｚ，ＣＤＣｌ３）：δ２８．１６，２８．２４，２８．８，２８．９，２９．０，２９．６，３６．２，４０．０，１１０．３，１１１．３，１２１．９，１２５．９，１２８．０，１３６．５；
ＩＲ（ＫＢｒ）：２９２２，２８４７，１４６３，１４４４，１２５９，１１２０，８８９，７７３，７３４，６７５，４１６，ｃｍ−１；
ＭＳｍ／ｚ６０４（Ｍ＋）；
Ａｎａｌ．Ｃａｌｃｄ．ｆｏｒＣ１６Ｈ１２Ｎ２Ｓ８：Ｃ，５１．６１；Ｈ，６．００％．Ｆｏｕｎｄ：Ｃ，５１．２９；Ｈ，５．８５％．
【００２５】
［実施例３］
冷却環を備えた枝付きフラスコ５０ｍｌに窒素気流下トリエチルホスファイト２５ｍｌを加えて油浴で１２０℃まで加熱した。このリアクターに合成例３で得たフェナントロ［９，１０−ｄ］１，３−ジチオレン−２−チオン１．４２２ｇ（５ｍｍｏｌ）と合成例４で得た４−（２−シアノエチルチオ）−５−メチルチオ−１，３−ジチオール−２−オン１．３２７ｇ（５ｍｍｏｌ）を一気に添加し、油浴で１．５時間攪拌した。反応溶液を室温まで冷やして吸引ろ過し、メタノールで洗浄した。１００℃で吸引ポンプにより乾燥し、クロロホルムを展開溶媒としてシリカゲルカラムクロマトグラフィー（φ＝５．０ｃｍ，ｈ＝１０ｃｍ）により分離精製して４−（２−シアノエチルチオ）−５−メチルチオ−フェナントロテトラチアフルバレン１．１０５ｇ（４６％）を橙色結晶として得た。この化合物の物性を以下に示す。
融点：１８３．５−１８４．２℃；
１ＨＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）：δ２．５３（ｓ，３Ｈ，ＣＨ３），２．７４（ｔ，Ｊ＝７．２Ｈｚ，４Ｈ，ＣＨ２），３．７２（ｔ，Ｊ＝７．２Ｈｚ，４Ｈ，ＣＨ２），７．６３−７．６６（ｍ，６Ｈ，Ａｒ−Ｈ），８．６４−８．６６（ｍ，４Ｈ，Ａｒ−Ｈ）；
１３ＣＮＭＲ（１０１ＭＨｚ，ＣＤＣｌ３）：δ１８．７，１９．１，３１．３，１０８．８，１１２．９，１１７．６，１２０．１，１２３．３（２Ｃ），１２５．７７，１２５．８２，１２６．７１，１２６．７４，１２６．９（２Ｃ），１２７．６９，１２７．７３，１２９．４（２Ｃ），１３０．９６，１３１．０５，１３５．３；
ＩＲ（ＫＢｒ）：３６５２，３０５５，２９２０，２２４８（ＣＮ），１６０６，１５７５，１４８８，１４４７，１４２７，１３４８，１３１９，１２８０，１２２３，１１４８，１０４３，９６３，９１３，８９９，７７７，７５０，７１６，６４７，６２０，５２５ｃｍ−１；
ＭＳｍ／ｚ４８５（Ｍ＋）；
Ａｎａｌ．Ｃａｌｃｄ．ｆｏｒＣ２２Ｈ１５ＮＳ６：Ｃ，５４．４０；Ｈ，３．１１；Ｎ，２．８８％．Ｆｏｕｎｄ：Ｃ，５４．４１；Ｈ，３．１３；Ｎ，２．８８％．
【００２６】
４−（２−シアノエチルチオ）−５−メチルチオ−フェナントロテトラチアフルバレン１４５ｍｇ（０．３ｍｍｏｌ）のＴＨＦ溶液１０ｍｌに１，８−ジブロモオクタン０．９２ｍｌ（５ｍｍｏｌ）を加え、水酸化セシウム７５ｍｇ（０．５ｍｍｏｌ）をメタノール５ｍｌに溶解した溶液を攪拌しながら滴下しさらに２時間室温にて攪拌した。塩化メチレンにより抽出し、乾燥剤を加えて残りの水を除去してろ別した。ロータリーエバポレーターにて濃縮して、クロロホルム：ｎ−ヘキサン（＝１：３）を展開溶媒としたシリカゲルカラムクロマトグラフィー（φ＝３．５ｃｍ，ｈ＝１５ｃｍ）およびゲルろ過クロマトグラフィーにより分離精製して４−（８−ブロモオクチルチオ）−５−メチルチオ−フェナントロテトラチアフルバレン１６５ｍｇ（８８％）を橙色結晶として得た。この化合物の物性を以下に示す。
融点：１００．１−１００．７℃
１ＨＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）：δ１．２９−１．８６（ｍ，１２Ｈ，ＣＨ２），２．４７（ｓ，１Ｈ，Ｓ−ＣＨ３），２．８６（ｔ，Ｊ＝７．３Ｈｚ，２Ｈ，Ｓ−ＣＨ２），３．３７（ｔ，Ｊ＝６．９Ｈｚ，２Ｈ，Ｂｒ−ＣＨ２），７．５９−７．６２（ｍ，６Ｈ，Ａｒ−Ｈ），８．５８−８．６１（ｍ，２Ｈ，Ａｒ−Ｈ）；
１３ＣＮＭＲ（１０１ＭＨｚ，ＣＤＣｌ３）：δ１９．３，２８．１，２８．３，２８．６，２８．９，３０．０，３２．７，３４．０，３６．２，１０８．９，１２３．３（２Ｃ），１２５．８（２Ｃ），１２６．０，１２６．６（２Ｃ），１２６．８（２Ｃ），１２７．６（２Ｃ），１２９．３，１２９．５，１３１．０８，１３１．１３；
ＩＲ（ＫＢｒ）：２９２９，２８５３，１６０７，１５７６，１４８７，１４６７，１４２７，１２９４，１２４６，１０４３，９６８，９１２，８９７，７７６，７４７，７１５，６４４，５２５，４２７ｃｍ−１；
Ａｎａｌ．Ｃａｌｃｄ．ｆｏｒＣ１９Ｈ２３ＢｒＳ６：Ｃ，５１．９９；Ｈ，４．３６％．Ｆｏｕｎｄ：Ｃ，５２．２２；Ｈ，４．６１％．
【００２７】
玉突き冷却環を備えた５０ｍｌ枝付きフラスコに４−（８−ブロモオクチルチオ）−５−メチルチオ−フェナントロテトラチアフルバレン０．４９９ｇ（０．８ｍｍｏｌ）のＴＨＦ溶液２０ｍｌを加え、さらにチオ尿素０．３０４ｇ（２．５ｍｍｏｌ）の水溶液５ｍｌを加えて２４時間還流した後、さらに水酸化ナトリウム０．４８０ｇ（１２ｍｍｏｌ）の水溶液５ｍｌを加え２時間還流した。次いで塩化メチレンに溶解して有機相を抽出し（ｐＨ１）、乾燥剤を加えて残りの水を除去してろ別した。引き続きロータリーエバポレーターにて濃縮して、クロロホルム：ｎ−ヘキサン（１：２）を展開溶媒としたシリカゲルカラムクロマトグラフィー（φ＝３．０ｃｍ，ｈ＝５ｃｍ）およびゲルろ過カラムクロマトグラフィーにより分離精製して４−（８−メルカプトオクチルチオ）−５−メチルチオ−フェナントロテトラチアフルバレン０．３８３ｇ（８３．０％）を橙色結晶として得た。この化合物の物性を以下に示す。
融点：８０．９−８１．８℃；
１ＨＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）：δ１．２９−１．７０（ｍ，１３Ｈ，ＣＨ２，ＳＨ），２．４５−２．４９（ｍ，５Ｈ，ＣＨ３，Ｓ−ＣＨ２），２．８６（ｔ，Ｊ＝７．３Ｈｚ，２Ｈ，Ｓ−ＣＨ２），７．６１−７．６３（ｍ，６Ｈ，Ａｒ−Ｈ），８．６０−８．６２（ｍ，２Ｈ，Ａｒ−Ｈ）；
１３ＣＮＭＲ（１０１ＭＨｚ，ＣＤＣｌ３）：δ１９．３，２４．６，２８．２５，２８．３３，２８．９０，２８．９３，２９．６７，３０．４，３４．０，３６．３，１１０．３，１１０．８，１２３．３（２Ｃ），１２５．８（２Ｃ），１２６．１，１２６．６（２Ｃ），１２６．９（２Ｃ），１２７．６（２Ｃ），１２９．４，１２９．５，１３１．１０，１３１．１５，１３６．４；
ＩＲ（ｎｅａｔ）３０５５，２９２３，２８５１，２５５３（ＳＨ），１６０７，１５７５，１４８８，１４６２，１４４７，１４２８，１２９４，１２３９，１２２１，１０４４，９６６，９１２，８９２，７７６，７４８，７１５，６４６，６２０，５２４，４２７ｃｍ−１；
ＭＳｍ／ｚ５７７（Ｍ＋）；
Ａｎａｌ．Ｃａｌｃｄ．ｆｏｒＣ１９Ｈ２４ＮＳ７：Ｃ，５６．２１；Ｈ，４．８９％．Ｆｏｕｎｄ：Ｃ，５６．１１；Ｈ，４．９０％．
【００２８】
［実施例４］
化合物（５）（ｎ＝８，ｍ＝０）で示されるテトラチアフルバレン誘導体の１ｍｍｏｌ／ｌ塩化メチレン溶液に作用極となる金電極を１２時間浸漬し、塩化メチレン、アセトンで洗浄し、アルゴンガスで乾燥した。この修飾電極を、過塩素酸テトラ‐ｎ‐ブチルアンモニウムの０．１ｍｏｌ／ｌベンゾニトリル溶液に、対電極として白金電極、参照電極としてＡｇ／ＡｇＮＯ３電極と共に浸漬した。比較電極に対して作用電極に−０．２Ｖから＋０．８Ｖの範囲で、走引速度は５００ｍＶ／ｓｅｃで電位を走引しサイクリックボルタングラフィーによる測定を行った。得られたサイクリックボルタモグラムより、本化合物は電位走査に伴い可逆な独立した二電子酸化・還元過程を示した。その酸化還元電位を表１に示す。
また、比較例として、「Ｌａｎｇｍｕｉｒ、１９９９，１５，８５７４−８５７６」に記載の化合物の酸化還元電位も示す。
【００２９】
［実施例５］
テトラチアフルバレン誘導体として化合物（６）（ｎ＝８）で示されるものを用いた以外は実施例４と同様にして電気化学的測定を行った。その酸化還元電位を表１に示す。
【００３０】
［実施例６］
テトラチアフルバレン誘導体として化合物（７）（ｎ＝８，ｍ＝０）で示されるものを用い、走引速度を１００ｍＶ／ｓｅｃとした以外は実施例４と同様にして電気化学的測定を行った。その酸化還元電位を表１に示す。
【００３１】
【表１】
【発明の効果】
本発明化合物の新規テトラチアフルバレン誘導体は、薄膜材料として有効であり、ダイオード、トランジスター、電極材料、配線材料、回路形成材料、EL材料等として好適である。
本発明化合物を用いた薄膜の製造法において、それを特に一定方向の磁場中で行うことにより、芳香環の磁気異方性に由来する配向制御を容易に発現させることができ、高密度、高配向の超薄膜を形成することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention is a novel tetrahedral compound having an aromatic ring and a thiol group or a disulfide group that is suitable as a thin film material such as a diode, transistor, electrode material, wiring material, circuit forming material, EL material, etc. The present invention relates to a thiafulvalene derivative and a method for producing the same.
[0002]
[Prior art]
Tetrathiafulvalene (TTF) is known to be a strong electron donor and forms a charge transfer complex with tetracyanoquinodimethane (TCNQ), which is an electron acceptor. It is known to have Also, practical devices such as incorporating functional organic molecules such as bisethylenedithiotetrathiafulvalene (BEDT-TTF) exhibiting superconductivity as electronic devices and using them as responsive elements utilizing their molecular recognition capabilities. In recent years, research on application of these has been actively conducted.
In addition, research on molecular recognition on metal and semiconductor surfaces and the structure of molecular aggregates is also active, and organic ultrathin films with controlled orientation, which are essential for creating practical devices that maximize the functions of organic molecules. A lot of research has been done on the production.
On the other hand, a study has been conducted to form a self-assembled film (SAM) on a smooth gold substrate or gold colloid for a TTF derivative having an alkanethiol group introduced into the TTF skeleton (Chem. Commun. 1999, 737 .; Langmuir, 1999, 15, 8574). However, a high-density, highly-oriented organic thin film has not yet been formed, and further development as a self-assembled film material is necessary.
On the other hand, as organic molecules, it is known that polycyclic aromatic compounds such as benzene, naphthalene, anthracene, phenanthrene, triphenylene, pyrene, and perylene have a large magnetic anisotropy as compared with ordinary ones. These compounds are also known to have functions such as photoconductivity, and attempts have been made to apply them to electronic devices as semiconductors.
[0003]
[Problems to be solved by the invention]
Based on these facts, it is expected that a compound having both an aromatic compound such as a benzene ring and a TTF skeleton can simultaneously exhibit a composite function such as an optical function and an electrical function. It is expected that an ultrathin film with high density and high orientation will be formed by producing a thin film in a magnetic field using the directivity.
Accordingly, an object of the present invention is to provide a novel tetrathiafulvalene derivative incorporating an aromatic ring serving as a magnetic anisotropy unit and a thiol group or a disulfide group, and further using it as a thin film material to provide a magnetic field. It is an object of the present invention to provide a method for producing a high-density, highly-oriented thin film.
[0004]
[Means for Solving the Problems]
In order to achieve the above object, the present invention (Claim 1)
General formula (2)
[Chemical 6]
General formula (3)
[Chemical 7]
Or
[Chemical 8]
General formula (1)
[Chemical formula 5]
It is a manufacturing method of the tetrathiafulvalene derivative represented by these.
The present invention (Claim 2)
General formula (1)
[Chemical formula 5]
It is a tetrathiafulvalene derivative represented by.
[0005]
The present invention (Claim 3) is a thin film body of a tetrathiafulvalene derivative characterized by having magnetic anisotropy obtained by coating the tetrathiafulvalene derivative according to claim 2 on a substrate.
The present invention (Claim 4)
General formula (1)
[Chemical formula 5]
Further, the present invention (Claim 5) is characterized in that when the thin film of the tetrathiafulvalene derivative according to Claim 3 or 4 is produced, the thin film is produced by applying a magnetic field in a certain direction. A method for producing a thin film of a derivative.
[0006]
BEST MODE FOR CARRYING OUT THE INVENTION
The tetrathiafulvalene derivative of the present invention (hereinafter referred to as the compound of the present invention) is represented by the above compound (1), and the aromatic ring in the general formula (1) is a formula
[Chemical 9]
Examples of R1 substituted on the aromatic ring include protons, alkyl groups such as methyl group / ethyl group, and alkoxy groups such as methoxy group and ethoxy group, and these are aromatic groups in the general formula (1). A plurality of the aromatic rings may be substituted.
[0007]
Specific examples of the compounds of claims 1 and 2 of the present invention include the following.
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The compound of the present invention can be obtained by reacting the thiones or ketones represented by the general formula (2) with the ketones represented by the general formula (3) or the general formula (4).
The reaction is carried out using an appropriate solvent such as an aromatic hydrocarbon solvent, THF, acetonitrile, DMF, disulfide carbon, water, hydrogen halide solvent such as triethyl phosphite, acetic acid, chloroform, alcohol solvent, etc., open system or inert gas It was performed under an air current. The preferred reaction temperature is -30 ° C to 250 ° C, more preferably 0 ° C to 150 ° C.
The thiones represented by the general formula (2) of the raw material compound are represented by the general formula
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[0009]
Moreover, this invention provides the thin film body which coat | covered the tetrathiafulvalene derivative of the said General formula (1) on the board | substrate.
Such a thin film body is suitable as a diode, a transistor, an electrode material, a wiring material, a circuit forming material, an EL material, or the like.
Examples of the method for producing the thin film include a vapor phase method in which the compound of the general formula (1) is vacuum-deposited, and a method by self-organization in a wet method to form a solution.
Moreover, when manufacturing a thin film using the tetrathiafulvalene derivative of the general formula (1), it is preferable to carry out in a magnetic field in a fixed direction because a high-density and highly-oriented one can be obtained.
[0010]
【Example】
EXAMPLES Next, although an Example demonstrates this invention further in detail, in addition, this invention is not limited at all by these examples.
[0011]
The synthesis of the thiones represented by the general formula (2) of the raw material compound will be described.
[Synthesis Example 1]
In a 500 ml eggplant flask with branches, N, N, N ′, N′-tetramethylenediamine (111 ml, 744 mmol) and n-hexane (300 ml) were added and stirred under a nitrogen stream, and n-butyllithium (300 ml, 744 mmol) was added and further stirred. did. To this reactor cooled to 0 ° C., 150 ml of an n-hexane solution of 34.11 ml (338 mmol) of thiophenol in a 200 ml flask with a branch joint was dropped with a cannula under a nitrogen stream. After dropping, the mixture was stirred at room temperature for 24 hours. Next, after cooling to 0 ° C., 23.86 g (744 mmol) of elemental sulfur was added and stirred at room temperature for 12 hours. After removing the solvent with a rotary evaporator, it was dissolved in 200 ml of pre-dried THF, cooled to 0 ° C., reduced with 10 g of lithium aluminum hydride, and refluxed as it was in an oil bath. After 2 hours, the solution was slowly poured into a beaker containing ice water, washed with ether and concentrated hydrochloric acid, extracted under acidic conditions, and the aqueous phase was removed. A sodium hydroxide aqueous solution (1N) was added to the organic phase remaining in the separatory funnel, and extraction was performed under basic conditions. At this time, the separated aqueous phase was added to a 500 ml eggplant flask, 6 g of sodium hydroxide and 80 ml of carbon disulfide were added, and the mixture was refluxed at a bath temperature of 60 ° C. After 6 hours, the bath temperature was raised to 100 ° C., and the cock of the fractional reflux reactor was opened to completely remove carbon disulfide. After cooling to room temperature, the crystals were separated by suction filtration and washed with water until the redness disappeared. The mixture was dried with a suction pump at 100 ° C. for 4 hours to remove water to obtain 55.84 g (90%) of 1,3-benzodithiol-2-thione as a yellow powder. The physical properties of this compound are shown below.
Melting point: 165.3-166.2 ° C;
1HNMR (400 MHz, CDCl3): Δ 7.38-7.50 (m, 4H, Ar-H);
13CNMR (101 MHz, CDCl3): Δ 121.8, 127.4, 141.3, 211.8;
UV (CHCl3) (Λmax (log ε)): 291.0 nm (4.11), 365.5 nm (4.76).
[0012]
[Synthesis Example 2]
The dried metal magnesium 1.094 g (45 mmol) was put into a 100 ml three-necked flask purged with nitrogen, and 8 ml of anhydrous THF was added and subjected to ultrasonic waves. After confirming the reaction by adding a few drops of ethylene dibromide as an initiator, 30 ml of a THF solution of 7.784 g (30 mmol) of 9-bromophenanthrene prepared in a 50 ml branch flask purged with nitrogen was added dropwise with a cannula. After completion of the reaction, the mixture was cooled to 0 ° C., 1.455 g (45 mmol) of simple sulfur was added, and the mixture was stirred for 12 hours at room temperature. Pour into a beaker containing ice water and dissolve the remaining magnesium with concentrated hydrochloric acid. The precipitate was separated by suction filtration, and the filtrate was extracted with methylene chloride, dried over magnesium sulfate, filtered, concentrated by a rotary evaporator, and dissolved in 150 ml of THF preliminarily dried together with the filter cake. The mixture was cooled to 0 ° C., 2 g of lithium aluminum hydride was added and refluxed for 2 hours, poured into a beaker containing ice water, adjusted to pH 1 with concentrated hydrochloric acid and extracted with a mixed solvent of ether and THF, and the aqueous phase was removed. An appropriate amount of 1N aqueous sodium hydroxide solution was added to the obtained organic phase for extraction, and the organic phase was removed. Concentrated hydrochloric acid was again added to the separated aqueous phase, extracted with methylene chloride, dried over magnesium sulfate, filtered, concentrated with a rotary evaporator, and silica gel column chromatography (φ = 5.0 cm) using chloroform as a developing solvent. , H = 3 cm) to obtain 5.04 g (80%) of 9-mercaptophenanthrene as a colorless powder. The physical properties of this compound are shown below.
Melting point: 97.0-98.0 ° C;
1HNMR (60 MHz, CDCl3): Δ 3.61 (s, 1H, SH), 7.48-7.85 (m, 6H, Ar—H), 8.14-8.36 (m, 1H, Ar—H), 8.45 −8.83 (m, 2H, Ar—H);
IR (KBr): 2566 (SH) cm-1
[0013]
In a 500 ml eggplant flask incorporating a branch joint, 9.72 g (70 mmol) of 9-mercaptophenanthrene, 250 ml of c-hexane and 23.1 ml (154 mmol) of N, N, N ′, N′-tetramethylenediamine were added in a nitrogen stream. After adding and stirring and cooling to 0 ° C., 62.6 ml (154 mmol) of n-butyllithium / n-hexane solution was added and stirred at room temperature for 24 hours. After further cooling to 0 ° C., 4.94 g (154 mmol) of elemental sulfur was added and stirred at room temperature for 12 hours. After removing the solvent with a rotary evaporator, it was dissolved in 300 ml of pre-dried THF, cooled to 0 ° C., reduced with 10.0 g of lithium aluminum hydride, and refluxed in an oil bath as it was. After 2 hours, the solution was slowly poured into a beaker containing ice water, washed with ether and concentrated hydrochloric acid, extracted under acidic conditions, and the aqueous phase was removed. A sodium hydroxide aqueous solution (5N) was added to the organic phase remaining in the separatory funnel, and extraction was performed under basic conditions. At this time, the separated aqueous phase was added to a 500 ml eggplant flask, 6 g of sodium hydroxide and 80 ml of carbon disulfide were added, and the mixture was refluxed at a bath temperature of 60 ° C. After 2 hours, the bath temperature was increased to 100 ° C., and the cock of the fractional reflux reactor was opened to completely remove carbon disulfide. As a result, yellow crystals were precipitated in the aqueous phase, and the crystals were separated by suction filtration and washed thoroughly with water. The mixture was dried with a suction pump at 100 ° C. for 2 hours to remove water. Chloroform was added to make a suspension solution, and the crystals were separated by suction filtration and washed thoroughly with chloroform. The filtrate collected by this operation was concentrated and crystals were taken out in the same manner several times. The separated crystals were subjected to filtration column treatment in suspension with a large amount of dichloromethane added. Concentration and drying gave 1.05 g (12%) of phenanthro [9,10-d] 1,3-dithiolene-2-thione as a yellow powder. The physical properties of this compound are shown below.
Melting point: 245.9-246.5 ° C;
1HNMR (400 MHz, CDCl3): Δ 7.65-7.75 (m, 6H, Ar-H), 8.68-8.70 (m, 2H, Ar-H);
1HNMR (400 MHz, CDCl3: CS2= 1: 10 (vol)): [delta] 7.59-7.69 (m, 6H, Ar-H), 8.59-8.62 (m, 2H, Ar-H);
13CNMR (101 MHz, CDCl3: CS2= 1: 10 (vol)): δ 67.4, 123.3 (2C), 125.4 (2C), 125.7, 127.4 (2C), 127.7 (2C), 129.1 (2C) ), 136.7 (2C);
IR (KBr): 1605, 1562, 1490, 1432, 1262, 1058, 803, 732, 717, 559, 519, 439, 436 cm-1;
MS m / z 284 (M+); Anal. Calcd. forC15H8S3: C, 63.34; H, 2.84%. Found: C, 63.63; H, 2.81%.
[0014]
It shows about the synthesis | combination of ketones represented by General formula (3) of a raw material compound.
[Synthesis Example 3]
To a flask purged with nitrogen, 4.6 g (200 mmol) of sodium and 36 ml (772 mmol) of carbon disulfide were added and refluxed for 30 minutes to activate sodium. Then, 40 ml of DMF was added and the mixture was refluxed again for 2 hours. The solvent was removed by distillation under reduced pressure in an oil bath. Next, the product was dissolved in 120 ml of methanol and 60 ml of water, 4 g (29.4 mmol) of zinc chloride and 75 ml of aqueous ammonia were added, and an aqueous solution of 10.6 g (50.4 mmol) of tetraethylammonium bromide was added. The product obtained by stirring and suction filtration was dried under reduced pressure at 80 ° C. for 12 hours and bis (tetraethylammonium) bis (2-thioxo-1,3-dithiol-4,5-dithiolate) zincate 15.95 g (88 %) As dark red crystals. The physical properties of this zinc complex compound are shown below.
Melting point: 198.7-200.1 ° C;
IR (KBr): 2979, 1458, 1417, 1182, 1059, 1038, 996, 888, 785 cm-1
[0015]
To 25 ml of acetonitrile, 1.44 g (2 mmol) of the zinc complex compound and 1.34 g (10 mmol) of 3-bromopropionitrile were added and refluxed for 1 hour. Next, the mixture was cooled to room temperature, the black precipitate was removed by suction filtration, the solvent was removed with a rotary evaporator, and the mixture was again dissolved in methylene chloride and extracted. Residual moisture was removed with a desiccant, and the desiccant was filtered off and concentrated with a rotary evaporator. Recrystallized with methylene chloride / n-hexane, filtered by suction, dried with a suction pump for 30 minutes, and 1.01 g of 4,5-bis (2-cyanoethylthio) -1,3-dithiol-2-thione (83%) was obtained as red needles. The physical properties of this compound are shown below.
Melting point 82.4-83.3 ° C .;
1HNMR (400 MHz, CDCl3): Δ 2.81 (t, J = 6.9 Hz, 4H, CH2), 3.17 (t, J = 6.9 Hz, 4H, CH2);
13CNMR (101 MHz, CDCl3): Δ 19.0, 31.8, 117.1, 135.8, 209.1;
IR (KBr): 2977, 2248, 1458, 1411, 1290, 1071, 894 cm-1
[0016]
The above solution of 4,5-bis (2-cyanoethylthio) -1,3-dithiol-2-thione dissolved in acetonitrile was stirred with a solution of 1.26 g (8.4 mmol) of cesium hydroxide dissolved in 12 ml of methanol. The solution was slowly added dropwise while stirring. After 30 minutes from the end of dropping, 11.36 g (40 mmol) of methyl iodide was added and stirred again for 30 minutes. In order to remove excess methyl iodide, nitrogen was blown in for 30 minutes and the mixture was concentrated on a rotary evaporator. The concentrate was dissolved in methyl chloride and extracted. After adding a desiccant to remove the remaining water, the concentrate was filtered off. Next, the mixture was concentrated on a rotary evaporator, separated and purified by silica gel column chromatography (φ = 5.5 cm, h = 16 cm) using chloroform as a developing solvent, and 4- (2-cyanoethylthio) -5-methylthio-1,3- 1.78 g (84%) of dithiol-2-thione was obtained as yellow needles. The physical properties of this compound are shown below.
Melting point 90.0-91.1 ° C .;
1HNMR (400 MHz, CDCl3): Δ2.56 (s, 3H, CH3), 2.75 (t, J = 7.1 Hz, 2H, CH2), 3.09 (t, J = 7.1 Hz, 2H, CH2);
13CNMR (101 MHz, CDCl3): Δ 18.8, 18.9, 31.8, 117.1, 126.0, 144.9, 209.9;
IR (KBr): 2247, 1464, 1438, 1416, 1318, 1276, 1054, 953, 900 cm-1
[0017]
[Synthesis Example 4]
1.59 g (6 mmol) of 4- (2-cyanoethylthio) -5-methylthio-1,3-dithiol-2-thione was replaced with nitrogen, and dissolved in 25 ml of a mixed solvent of chloroform / acetic acid (3: 1). Using a solid addition device, 5 g (16 mmol) of mercury acetate substituted with nitrogen was added, and after stirring for 16 hours, the filtrate was separated by suction filtration. This was poured into a beaker, neutralized with a saturated aqueous sodium hydrogen carbonate solution, and extracted with a separatory funnel. The remaining water was removed with a desiccant and filtered. The mixture was concentrated with a rotary evaporator and dried with a suction pump to quantitatively obtain 1.57 g of 4- (2-cyanoethylthio) -5-methylthio-1,3-dithiol-2-one as yellow needles. The physical properties of this compound are shown below.
Melting point 61.8-62.5 ° C .;
1HNMR (400 MHz, CDCl3): Δ2.52 (s, 3H, CH3), 2.74 (t, J = 7.1 Hz, 2H, CH2), 3.07 (t, J = 7.1 Hz, 2H, CH2);
13CNMR (101 MHz, CDCl3): Δ 18.8, 19.1, 31.6, 117.2, 118.0, 135.6, 188.7;
IR (KBr): 2922, 2246, 1777, 1661, 1618, 1413, 1274, 957, 899, 747 cm-1
[0018]
[Synthesis Example 5]
0.913 g (3 mmol) of 4,5-bis (2-cyanoethylthio) -1,3-dithiol-2-thione was replaced with nitrogen and dissolved in 25 ml of a mixed solvent of chloroform / acetic acid (3: 1). Mercury acetate 2.500 g (8 mmol) was added using a solid addition apparatus, and after stirring for 16 hours, the filtrate was separated by suction filtration. This was poured into a beaker, neutralized with a saturated aqueous sodium hydrogen carbonate solution, and extracted with a separatory funnel. The remaining water was removed with a desiccant and filtered. The solution was concentrated with a rotary evaporator and dried with a suction pump to quantitatively obtain 0.921 g of 4,5-bis (2-cyanoethylthio) -1,3-dithiol-2-one as deep yellow needles. The physical properties of this compound are shown below.
Melting point: 62.8-64.2 ° C;
1NMR (400 MHz, CDCl3): Δ 2.80 (t, J = 6.9 Hz, 4H, CH2), 3.14 (t, J = 6.9 Hz, 4H, CH2);
13CNMR (101 MHz, CDCl3): Δ 19.0, 31.6, 117.2, 127.4, 187.6;
IR (KBr): 2951, 2249, 1775, 1666, 1615, 1420, 1283, 1156, 886, 741 cm-1
[0019]
[Example 1]
0.92 g (5 mmol) of 1,3-benzodithiol-2-thione obtained in Synthesis Example 1 and 4- (2-cyanoethylthio) -5-methylthio-1,3-dithiol-2- obtained in Synthesis Example 4 1.42 g (5 mmol) of ON was substituted with nitrogen, 6.4 ml of triethyl phosphite was added, and the mixture was stirred at 120 ° C. for 1.5 hours. The reaction solution was cooled to room temperature, and the crystals were separated by suction filtration and washed with methanol. Separation and purification by silica gel column chromatography (φ = 3.0 cm, h = 3 cm) using chloroform as a developing solvent gave 1.06 g (68%) of 4- (2-cyanoethylthio) -5-methylthio-benzotetrathiafulvalene. Obtained as orange needles. The physical properties of this compound are shown below.
In addition, 1,3-benzodithiol-2-one represented by the general formula (2) and 4- (2-cyanoethylthio) -5-methylthio-1,3-dithiol-2-one obtained in Synthesis Example 4 Similarly, 4- (2-cyanoethylthio) -5-methylthiobenzotetrathiafulvalene can be obtained in a yield of 18%.
Melting point 128.5-129.4 [deg.] C;
1HNMR (400 MHz, CDCl3): Δ 2.48 (s, 3H, CH3), 2.70 (t, J = 7.2 Hz, 4H, CH2), 3.03 (t, J = 7.2 Hz, 4H, CH2), 7.11-7.27 (m, 4H, Ar-H);
13CNMR (101 MHz, CDCl3): Δ 18.7, 19.1, 31.2, 108.5, 113.4, 117.5, 120.0, 121.91, 121.93, 126.02, 126.03, 135.1, 136.2, 136.3;
IR (KBr): 2920, 2246, 1493, 1444, 1415, 1272, 1120, 896, 774, 741, 731, 674 cm-1
MS m / z 385 (M+);
Anal. Calcd. forC14H11NS6: C, 43.60; H, 2.88; N, 3.63%. Found: C, 43.24; H, 2.87; N, 3.67%.
[0020]
1.84 ml (10 mmol) of 1,8-dibromooctane was added to 20 ml of THF solution of 771 mg (2 mmol) of 4- (2-cyanoethylthio) -5-methylthio-benzotetrathiafulvalene, and 450 mg (3 mmol) of cesium hydroxide was added. A solution dissolved in 10 ml of methanol was added dropwise with stirring, and the mixture was stirred at room temperature for 3 hours. Extraction was performed by dissolving in methylene chloride, and a desiccant was added to remove the remaining water, followed by filtration. Subsequently, the mixture was concentrated on a rotary evaporator and separated and purified by silica gel column chromatography (φ = 3.5 cm, h = 10 cm) and gel filtration chromatography using chloroform: n-hexane (= 1: 2) as a developing solvent. 890 mg (85%) of 4- (8-bromooctylthio) -5-methylthio-benzotetrathiafulvalene was obtained as an orange oil. The physical properties of this compound are shown below.
1HNMR (400 MHz, CDCl3): Δ 1.30-1.86 (m, 12H, CH2), 2.43 (s, 3H, CH3), 2.81 (t, J = 7.2 Hz, 2H, CH2), 3.39 (t, J = 6.8 Hz, 2H, CH2), 7.10-7.25 (m, 4H, Ar-H);
13CNMR (101 MHz, CDCl3): Δ19.2, 28.0, 28.2, 28.6, 28.8, 30.0, 32.7, 34.0, 36.2, 110.1, 111.3, 121.9, 125.8, 125.9, 136.48, 136.53;
IR (neat): 2927, 2853, 1447, 774, 559 cm-1;
MS m / z 523 (M+);
Anal. Calcd. forC19H23BrS6: C, 43.58; H, 4.43%. Found: C, 43.53; H, 4.69%.
[0021]
20 ml of a THF solution of 262 mg (0.5 mmol) of 4- (8-bromooctylthio) -5-methylthio-benzotetrathiafulvalene was added to a 50 ml branch flask equipped with a ball cooling ring, and 191 mg of thiourea (2. 5 ml of an aqueous solution of 5 mmol) was added and refluxed for 24 hours, and then 5 ml of an aqueous solution of 300 mg (15 mmol) of sodium hydroxide was added and refluxed for 2 hours. The product was dissolved in methylene chloride, the organic phase was extracted under acidic conditions, the desiccant was added and the remaining water was removed and filtered off. Subsequently, the mixture was concentrated on a rotary evaporator and separated and purified by silica gel column chromatography (φ = 3.0 cm, h = 5 cm) and gel filtration column chromatography using chloroform: n-hexane (1: 2) as a developing solvent. There was obtained 151 mg (63.3%) of-(8-mercaptooctylthio) -5-methylthio-benzotetrathiafulvalene as an orange oil. The physical properties of this compound are shown below.
1HNMR (400 MHz, CDCl3): Δ 1.29-1.66 (m, 13H, CH2, SH), 2.43 (s, 3H, CH3), 2.51 (q, J = 7.2 Hz, 2H, CH2), 2.82 (t, J = 7.2 Hz, 2H, CH2), 7.10-7.26 (m, 4H, Ar-H);
13CNMR (101 MHz, CDCl3): Δ19.2, 24.6, 28.2, 28.3, 28.88, 28.91, 29.6, 34.0, 36.2, 96.1, 110.2, 111.3, 121.9, 125.9, 129.3, 136.51, 136.55;
IR (neat): 2925, 2852, 2563, 1446, 774, 559 cm-1;
MS m / z 476 (M +);
Anal. Calcd. forC19H24NS7: C, 47.86; H, 5.07%. Found: C, 47.57; H, 5.11%.
[0022]
[Example 2]
0.922 g (5 mmol) of 1,3-benzodithiol-2-thione obtained in Synthesis Example 1 and 4,5-bis (2-cyanoethylthio) -1,3-dithiol-2-one obtained in Synthesis Example 5 1.422 g (5 mmol) was replaced with nitrogen, 6.4 ml of triethyl phosphite was added, and the mixture was stirred at 120 ° C. for 1.5 hours. The reaction solution was cooled to room temperature, and the crystals were separated by suction filtration and washed with methanol. Separation and purification by silica gel column chromatography (φ = 3.0 cm, h = 3 cm) using chloroform as a developing solvent to obtain 0.829 g (39%) of 4,5-bis (2-cyanoethylthio) -benzotetrathiafulvalene in orange Obtained as needles. The physical properties of this compound are shown below.
Melting point: 147.2-148.0 ° C;
1H NMR (400 MHz, CDCl3): Δ 2.74 (t, J = 7.1 Hz, 4H, CH2), 3.09 (t, J = 7.1 Hz, 4H, CH2), 7.13-7.28 (m, 4H, Ar-H);
13CNMR (101 MHz, CDCl3): Δ 18.8, 31.2, 106.9, 115.4, 117.4, 122.0, 126.1, 127.9, 136.1;
IR (KBr) 2925, 2251, 1426, 1119, 892, 735 cm-1;
MS m / z 424 (M +);
Anal. Calcd. forC16H12N2S6: C, 45.25; H, 2.85; N, 6.60%. Found: C, 45.04; H, 2.81; N, 6.52%.
[0023]
To a 30 ml THF solution of 425 mg (1 mmol) of 4,5-bis (2-cyanoethylthio) -benzotetrathiafulvalene, 3.68 ml (20 mmol) of 1,8-dibromooctane was added, and 330 mg of cesium hydroxide dissolved in 5 ml of methanol. (5 mmol) was added dropwise with stirring and the mixture was stirred at room temperature for 2 hours. The extract was dissolved in methylene chloride, extracted, added with a desiccant to remove the remaining water and filtered. Subsequently, the mixture was concentrated on a rotary evaporator and separated and purified by silica gel column chromatography (φ = 3.5 cm, h = 10 cm) and gel filtration chromatography using chloroform: n-hexane (= 1: 2) as a developing solvent. There were obtained 541 mg (77%) of 4,5-bis (8-bromooctylthio) -benzotetrathiafulvalene as an orange oil. The physical properties of this compound are shown below.
1HNMR (400 MHz, CDCl3): Δ1.32-1.87 (m, 24H, CH2), 2.88 (t, J = 7.3 Hz, 4H, CH2), 3.38 (t, J = 6.8 Hz, 4H, CH2), 7.09-7.26 (m, 4H, Ar-H);
13CNMR (101 MHz, CDCl3): Δ 28.1, 28.4, 28.7, 28.9, 29.8, 32.8, 34.0, 36.5, 121.87, 121.91, 125.9, 126.0, 131.7, 136.5, 136.6;
MS m / z 700 (M +);
Anal. Calcd. forC26H36Br2S6: C, 44.56; H, 5.18%. Found: C, 44.37; H, 5.44%.
[0024]
After adding 5 ml of an aqueous solution of 761 mg (5 mmol) of thiourea to a solution of 701 mg (1 mmol) of 4,5-bis (8-bromooctylthio) -benzotetrathiafulvalene in 20 ml of THF and stirring in an oil bath at 80 ° C. for 24 hours. Then, 10 ml of an aqueous solution of 1.2 mg (30 mmol) of sodium hydroxide was added and refluxed for 2 hours. After concentrating to some extent with a rotary evaporator, it was extracted by dissolving in methylene chloride under acidic conditions, and the remaining water was removed by filtration by adding a desiccant. 50 ml of this methylene chloride reaction solution was oxidized dropwise with methylene chloride solution of iodine and triethylamine, and extracted with an aqueous sodium hydrogen sulfite solution. Concentrate on a rotary evaporator and separate and purify by silica gel column chromatography (φ = 3.5 cm, h = 10 cm) using chloroform: n-hexane (1: 3) and recrystallization with chloroform: methanol. Then, 74 mg (12%) of a benzotetrathiafulvalene derivative represented by compound (6) (n = 8) was obtained as orange needle crystals. The physical properties of this compound are shown below.
Melting point: 83.9-84.2 ° C;
1HNMR (400 MHz, CDCl3): Δ1.32-1.71 (m, 24H, CH2), 2.66 (t, J = 7.3 Hz, 4H, SS-CH2), 3.39 (t, J = 7.3 Hz, 4H, CS-CH2), 7.10-7.26 (m, 4H, Ar-H);
13CNMR (101 MHz, CDCl3): Δ 28.16, 28.24, 28.8, 28.9, 29.0, 29.6, 36.2, 40.0, 110.3, 111.3, 121.9, 125.9, 128.0, 136.5;
IR (KBr): 2922, 2847, 1463, 1444, 1259, 1120, 889, 773, 734, 675, 416, cm-1;
MS m / z 604 (M+);
Anal. Calcd. forC16H12N2S8: C, 51.61; H, 6.00%. Found: C, 51.29; H, 5.85%.
[0025]
[Example 3]
25 ml of triethyl phosphite was added to 50 ml of a branch flask equipped with a cooling ring under a nitrogen stream and heated to 120 ° C. in an oil bath. To this reactor, 1.422 g (5 mmol) of phenanthro [9,10-d] 1,3-dithiolene-2-thione obtained in Synthesis Example 3 and 4- (2-cyanoethylthio) -5- 5 obtained in Synthesis Example 4 were added. 1.327 g (5 mmol) of methylthio-1,3-dithiol-2-one was added all at once and stirred in an oil bath for 1.5 hours. The reaction solution was cooled to room temperature, suction filtered, and washed with methanol. It is dried with a suction pump at 100 ° C., separated and purified by silica gel column chromatography (φ = 5.0 cm, h = 10 cm) using chloroform as a developing solvent, and 4- (2-cyanoethylthio) -5-methylthio-phenanthro. 1.105 g (46%) of tetrathiafulvalene was obtained as orange crystals. The physical properties of this compound are shown below.
Melting point: 183.5-184.2 ° C;
1HNMR (400 MHz, CDCl3): Δ2.53 (s, 3H, CH3), 2.74 (t, J = 7.2 Hz, 4H, CH2), 3.72 (t, J = 7.2 Hz, 4H, CH2), 7.63-7.66 (m, 6H, Ar-H), 8.64-8.66 (m, 4H, Ar-H);
13CNMR (101 MHz, CDCl3): Δ 18.7, 19.1, 31.3, 108.8, 112.9, 117.6, 120.1, 123.3 (2C), 125.77, 125.82, 126.71, 126 74, 126.9 (2C), 127.69, 127.73, 129.4 (2C), 130.96, 131.05, 135.3;
IR (KBr): 3652, 3055, 2920, 2248 (CN), 1606, 1575, 1488, 1447, 1427, 1348, 1319, 1280, 1223, 1148, 1043, 963, 913, 899, 777, 750, 716, 647, 620, 525cm-1;
MS m / z 485 (M+);
Anal. Calcd. forC22H15NS6: C, 54.40; H, 3.11; N, 2.88%. Found: C, 54.41; H, 3.13; N, 2.88%.
[0026]
To 10 ml of THF solution of 145 mg (0.3 mmol) of 4- (2-cyanoethylthio) -5-methylthio-phenanthrotetrathiafulvalene, 0.92 ml (5 mmol) of 1,8-dibromooctane was added, and 75 mg of cesium hydroxide ( 0.5 mmol) in 5 ml of methanol was added dropwise with stirring, and the mixture was further stirred at room temperature for 2 hours. Extraction was performed with methylene chloride, and a desiccant was added to remove the remaining water, followed by filtration. Concentrate with a rotary evaporator and separate and purify by silica gel column chromatography (φ = 3.5 cm, h = 15 cm) and gel filtration chromatography using chloroform: n-hexane (= 1: 3) as a developing solvent. 165 mg (88%) of-(8-bromooctylthio) -5-methylthio-phenanthrotetrathiafulvalene was obtained as orange crystals. The physical properties of this compound are shown below.
Melting point: 100.1-100.7 ° C
1HNMR (400 MHz, CDCl3): Δ 1.29-1.86 (m, 12H, CH2), 2.47 (s, 1H, S-CH3), 2.86 (t, J = 7.3 Hz, 2H, S-CH)2), 3.37 (t, J = 6.9 Hz, 2H, Br-CH2), 7.59-7.62 (m, 6H, Ar-H), 8.58-8.61 (m, 2H, Ar-H);
13CNMR (101 MHz, CDCl3): Δ 19.3, 28.1, 28.3, 28.6, 28.9, 30.0, 32.7, 34.0, 36.2, 108.9, 123.3 (2C), 125 .8 (2C), 126.0, 126.6 (2C), 126.8 (2C), 127.6 (2C), 129.3, 129.5, 131.08, 131.13;
IR (KBr): 2929, 2853, 1607, 1576, 1487, 1467, 1427, 1294, 1246, 1043, 968, 912, 897, 776, 747, 715, 644, 525, 427 cm-1;
Anal. Calcd. forC19H23BrS6: C, 51.99; H, 4.36%. Found: C, 52.22; H, 4.61%.
[0027]
20 ml of a THF solution of 0.499 g (0.8 mmol) of 4- (8-bromooctylthio) -5-methylthio-phenanthrotetrathiafulvalene was added to a 50 ml branch flask equipped with a ball cooling ring. After adding 5 ml of an aqueous solution of 304 g (2.5 mmol) and refluxing for 24 hours, 5 ml of an aqueous solution of 0.480 g (12 mmol) of sodium hydroxide was further added and refluxed for 2 hours. Subsequently, the organic phase was extracted by dissolving in methylene chloride (pH 1), and the remaining water was removed by filtration by adding a desiccant. Subsequently, the mixture was concentrated on a rotary evaporator and separated and purified by silica gel column chromatography (φ = 3.0 cm, h = 5 cm) and gel filtration column chromatography using chloroform: n-hexane (1: 2) as a developing solvent. There was obtained 0.383 g (83.0%) of 4- (8-mercaptooctylthio) -5-methylthio-phenanthrotetrathiafulvalene as orange crystals. The physical properties of this compound are shown below.
Melting point: 80.9-81.8 ° C;
1HNMR (400 MHz, CDCl3): Δ 1.29-1.70 (m, 13H, CH2, SH), 2.45-2.49 (m, 5H, CH3, S-CH2), 2.86 (t, J = 7.3 Hz, 2H, S-CH)2), 7.61-7.63 (m, 6H, Ar-H), 8.60-8.62 (m, 2H, Ar-H);
13CNMR (101 MHz, CDCl3): Δ 19.3, 24.6, 28.25, 28.33, 28.90, 28.93, 29.67, 30.4, 34.0, 36.3, 110.3, 110.8, 123.3 (2C), 125.8 (2C), 126.1, 126.6 (2C), 126.9 (2C), 127.6 (2C), 129.4, 129.5, 131.10 131.15, 136.4;
IR (neat) 3055, 2923, 2851, 2553 (SH), 1607, 1575, 1488, 1462, 1447, 1428, 1294, 1239, 1221, 1044, 966, 912, 892, 776, 748, 715, 646, 620 , 524, 427cm-1;
MS m / z 577 (M+);
Anal. Calcd. forC19H24NS7: C, 56.21; H, 4.89%. Found: C, 56.11; H, 4.90%.
[0028]
[Example 4]
A gold electrode as a working electrode is immersed in a 1 mmol / l methylene chloride solution of a tetrathiafulvalene derivative represented by compound (5) (n = 8, m = 0) for 12 hours, washed with methylene chloride and acetone, and argon gas. And dried. This modified electrode was added to a 0.1 mol / l benzonitrile solution of tetra-n-butylammonium perchlorate, a platinum electrode as a counter electrode, and Ag / AgNO as a reference electrode.3It was immersed with the electrode. Measurement was performed by cyclic voltamography while the potential was run at a working speed of 500 mV / sec in the range of −0.2 V to +0.8 V on the working electrode with respect to the comparative electrode. From the obtained cyclic voltammogram, this compound showed a reversible independent two-electron oxidation / reduction process with potential scanning. The oxidation-reduction potential is shown in Table 1.
In addition, as a comparative example, the oxidation-reduction potential of the compound described in “Langmuir, 1999, 15, 8574-8576” is also shown.
[0029]
[Example 5]
The electrochemical measurement was performed in the same manner as in Example 4 except that the compound represented by the compound (6) (n = 8) was used as the tetrathiafulvalene derivative. The oxidation-reduction potential is shown in Table 1.
[0030]
[Example 6]
An electrochemical measurement was performed in the same manner as in Example 4 except that a compound represented by the compound (7) (n = 8, m = 0) was used as the tetrathiafulvalene derivative and the running speed was set to 100 mV / sec. . The oxidation-reduction potential is shown in Table 1.
[0031]
[Table 1]
【The invention's effect】
The novel tetrathiafulvalene derivative of the compound of the present invention is effective as a thin film material and is suitable as a diode, transistor, electrode material, wiring material, circuit forming material, EL material and the like.
In the method for producing a thin film using the compound of the present invention, the orientation control derived from the magnetic anisotropy of the aromatic ring can be easily expressed by performing it in a magnetic field in a specific direction. An oriented ultra-thin film can be formed.
Claims (5)
一般式（３）
一般式（１）
で表わされるテトラチアフルバレン誘導体の製造方法。General formula (2)
General formula (3)
General formula (1)
The manufacturing method of the tetrathiafulvalene derivative represented by these.
で表わされるテトラチアフルバレン誘導体。General formula (1)
The tetrathiafulvalene derivative represented by these.
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